Production of detonatable explosive emulsion preparations



United States Patent 3,212,945 PRODUCTION OF DETONATABLE EXPLOSIVE EMULSION PREPARATIONS Adolf Berthmann and Clemens Franze, Leverkusen, and Paul Lingens, Cologne-Marienburg, Germany, assignors to Dynamit Nobel Aktiengesellschaft, Troisdorf, Bez. Cologne, Germany, a German corporation No Drawing. Filed May 21, 1962, Ser. No. 196,445 Claims priority, application Germany, May 24, 1961, D 36,160 14 Claims. (Cl. 14951) The present invention relates to improvements in detonatable explosion emulsion preparations, and more particularly to a water-in-oil emulsion of an aqueous solution, an emulsifier, and an explosive components.

Heretofore, Water alone has been added to gelatinous explosives, together with glue, dextrin, and starch, the latter three components being used to bind the water added. Also, emulsions have been of interest which include liquid nitric acid esters and water, but only with a view to solving the delicate transportation problems attendant with explosive materials. A particular possibility is known for the safe transportation of nitroglycerin, i.e., explosive oil generally of the nitric acid ester type, by conducting the nitroglycerin through a pipe line in the form of an emulsion produced with water. This conventional technique, using a water emulsion with nitroglycerin, as demonstrated by extensive tests, no longer presents such a condition that dangerous detonation may be propagated with respect to the explosive in question. Unfortunately, however, these emulsions may be kept stable only under quite specific flow conditions, as for example, those which exist in a flow pipe line positioned at an incline.

Therefore, many attempts have been made to improve upon explosive preparations whereby the same would be safe when transported, yet would provide the needed detonating properties at the end point of use. One attempt in this connection has been to increase the stability of emulsions of water with nitroglycerin by the incorporation of certain emulsifiers and even through the further inclusion of emulsifying auxiliary agents. Nevertheless, independently of the type of production procedure, the nitroglycerin-water-emulsion must possess as a prime condition, the ability to be transported safely in a manner that the preparation no longer possesses an explosive character, i.e., such preparation must no longer be capable of propagating a detonative conversion initiated at a given place. These known emulsions are oil-in-water type emulsions.

In accordance with the earlier filed co-pending US. application Serial No. 179,491, filed March 13, 1962, a detonatable explosive emulsion preparation is disclosed which comprises a water-in-oil emulsion of water, an emulsifier, and an explosive component, which may contain up to 72% water while the emulsifier may be present in an amount of from about 0.05 to 5% by weight based upon the total emulsion preparation, and preferably in an amount of about 1% by weight. A stabilizer for the explosive component may be included optionally in the emulsion preparation, as for example collodion cotton which is normally used for explosives, or polyvinylacetate, e.g. with about 20 monomers in the polymer chain. The explosive component of the preparation may be in the form of a liquid or a fused compound, such as nitroglycerin or trinitrotoluene.

In accordance with the disclosure of said co-pending application, the emulsifier used may be an ionic or nonionic substance. Specifically, the ionic substance may be a metal salt of a long-chain fatty acid, and more particularly a member selected from the group consisting 3,212,945 Patented Get. 19, 1965 of alkaline earth-, magnesium-, aluminum-, and zincsalts of the paraffin fatty acids, oleic acid, and the long chain of oxy-acids, such as the lithium, calcium, magnesium, aluminum, and zinc salts of stearic acid, palmetic acid, oxy-stearic acid, oleic acid, and other long-chain carboxylic acids, abietic acid, etc., and mixtures thereof. On the other hand, the non-ionic emulsifier substances may include a member selected from the group consisting of glycerin stearates, abietic acid derivatives, such as alkyl esters and metal salts, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, and esters of long-chain fatty acids with higher alcohols, such as lanolin, etc., and mixtures thereof.

In its broadest aspects, said co-pending application contemplates an aqueous emulsion capable of detonation in which the aqueous phase is emulsified. in the from of fine droplets in the explosive component... The water-inoil emulsion is produced actually with the aid of emulsifiers of water and liquid or fused explosive components, it being understood that regardless of the fact that the explosive component may be liquid or solid, suitably, such explosive component must be fusible. The particular emulsion preparation may be carried out in the conventional manner using the above-mentioned emulsifiers as they are added for the production of waterin-oil emulsions of the normal type. While the foregoing emulsions may contain up to 72% water, with the emulsifier substance concentration ranging between ODS-5%, based upon the emulsion, it is still possible to vary within a wide range the quantity of Water actually contained in the emulsion, Naturally, the stability of the water-in-oil emulsion is improved by the addition of a stabilizer, such as collodion-cotton.

The advantages of the foregoing emulsion preparation were demonstrated by examples in which the explosive properties of said foregoing water-in-oil type emulsions were compared with those of a known oil-in-water emulsion of nitroglycerin (explosive oil)/Water (type O/W). Thus, a water-in-oil emulsion produced from 50 cc. nitroglycerin (explosive oil, representing a mixture of 60 parts of nitroglycerin and 40 parts of nitroglycol), 50 cc. water and 0.5 grams zinc-oxy steareate with 0.5 gram collodion cotton as stabilizer, is capable of detanation and exhibited in the lead-block test according to Trauzl in a quantity of 10 grams, a bulging of 225 cubic centimeters, the emulsion having been detonated with a priming cap #8. While it is clear from such example that the foregoing water-inoil emulsion possesses absolutely the character of an explosive, in contrast thereto, an analogously composed emulsion, to which had been added, in place of the zinx oxy stearate and collodion cotton, corresponding quantities of sodium-cetyl sulfate and methyl cellulose as emulsifying agent 50 as to present an emulsion of the oil-in-water type, could no longer be detonated with a priming cap #8. Accordingly, the latter preparation did not exhibit any bulging of the lead-block as was the case with the emulsion prepared in accordance with said copending application, and therefore the typical oil-inwater emulsion of the conventional type cannot be considered an explosive. In the same way, using a Water-inoil emulsion of 75 cc. nitroglycerin (same type of explosive oil), 25 cc. water, 0.5 gram of partially acetylated polyvinyl alcohol, and 1 gram collodion cotton, a lead block bulging of 410 cubic centimeters Was obtained, the procedure being the same as above described. Where such procedure was followed with a water-in-oil emulsion of 50 cc. nitroglycerin (same type of explosive oil), 50 cc. Water, 0.5 gram magnesium-oleate, and 0.3 gram collodion cotton, a lead block bulging of 220 cubic centimeters Was obtained. In the case of a water-in-oil emulsion of 75 cc. nitroglycerin (same type of explosive oil),

25 cc. water, 0.5 gram calcium stearate, and 2 grams collodion cotton, such procedure lead to a lead block bulging of 415 cubic centimeters. Using such procedure with a water-in-oil emulsion of 45 cc. nitroglycerin (same type of explosive oil), 55 cc. water, 0.5 gram zinc stearate, and 2 grams collodion cotton, a lead block bulging of 215 cubic centimeters was obtained. On the other hand, where such procedure was followed with a water-in-oil emulsion of 40 cc. nitroglycerin (same type of explosive oil), 60 cc. water, 0.5 gram polyglycol monostearyl ether (Peregal O) and 2 grams collodion cotton, a lead block bulging of 110 cubic centimeters was obtained. Additionally, where the water-in-oil emulsion contained 35 cc. nitroglycerin (same type of explosive oil), 65 cc. water, 0.5 gram long-chain fatty acid of a higher alcohol (lanolin) and 1 gram collodion cotton, the foregoing procedure lead to a lead block bulging of 75 cubic centimeters, whereas with 30 cc. nitroglycerin (same type of explosive oil), 70 cc. water, 0.6 gram zinc-12-oxystearate and 1 gram collodion cotton, a lead block bulging 25 cubic centimeters was obtained.

The disclosure of said co-pending application illustrates further the effectiveness of water-in-oil emulsions, as for example where various TNT-H O-emulsions were produced at 90 C. using an addition of 0.5% collodion cotton and 1% calcium stearate, the so-prepared emulsions being poured into cardboard tubes having an inside diameter of 30 mm. Upon cooling, stable solid trinitrotoluene-water emulsions were obtained, and these were placed on lead slabs of 6 mm. thickness and tested by ignition with pressed tetryl (trinitrophenylmethylnitramine) at a dosage of 25 grams to determine the detonation capacity of the particular emulsions. The results illustrated that with 77.5% TNT and 21% H O, the detonation capacity and/ or brisance lead to the complete rupturing of the lead slab, whereas using a solid emulsion of 63.5% TNT and 35% H O, the lead slab was barely ruptured. On the other hand, using 46.5% TNT and 52% H O, the lead slab was strongly crushed-in while the lead slab was only barely crushed-in using 30.5% TNT and 68% H O.

The foregoing illustrations demonstrate the great advantage of emulsions capable of detonation, as produced in accordance with the disclosure of said co-pending application, to wit, the varying, almost at random, of the consistency of the mixtures of ingredients in question. By the particular selection of the amounts of the two liquids to be emulsified, and the quantity of the stabilizer desired, preparations are thus obtainable which are pourable, creamy, foamy, syrupy, pulpy, gelatinous, pasty, fat-like or wax-like, brittle, or massive solid masses. Thus, because of these characteristics, emulsion preparations may now be produced which are capable of detonation under the desired conditions but which are safe in transport as well, rending them widely applicable for industrial explosion practices. In this connection, as disclosed in said co-pending application, the characteristic of impact (percussion) sensitivity, and friction sensitivity may be varied within wide limits depending upon the amount of Water added to the emulsion, which properties would not have been expected in view of the fact that nitroglycerin is an explosive oil which is present in the emulsion as an undivided phase. Hence, a gelatin preparation of 100 cc. nitroglycerin (same type of explosive oil as noted above, i.e., 60/40), 1 gram collodion cotton, and 0.5 gram zinc-12-oxy stearate is detonatable using a drop hammer according to Kast (Posts Chemisch-Teclinische Analyse, 3rd ed. (1909), vol II, No. 3), using a 2 kg. weight and a dropping height of 60 centimeters. Where half the volume quantity of the nitroglycerin (explosive oil) present in the gelatin is replaced by water so as to form an oil-in-water emulsion, no explosive detonation is obtained even with a kg. weight and a dropping height of 60 centimeters.

All in all said co-pending application discloses that a particular water-in-oil emulsion of water, an emulsifier, and an explosive component may be provided which is safely transportable and still able to be detonated under reasonable detonating conditions at the point of end use, applying normal detonation impact values.

It is an object of the present invention to provide a detonatable explosive emulsion preparation similar to that disclosed in said co-pending application, which is also safe to transport in its prepared condition, yet which is capable of exerting the explosive force desired at the point of end use, the emulsion preparation in accordance with the present invention representing a modification in which the water component of the emulsion preparation is replaced with an aqueous solution of a water-soluble carbon-containing compound, and/ or a water-soluble oxygencontaining compound.

Other and further objects of the invention will become apparent from a study of the within specification and accompanying examples.

It has been found in accordance with the present invention that a detonatable explosive emulsion preparation may be provided which comprises a water-in-oil emulsion of an aqueous favourably saturated solution, an emulsifier, and an explosive component, wherein the aqueous solution used is a solution of at least one of a water-soluble carbon-containing compound and a water-soluble oxygencontaining compound, whereby safety in transport as well as effective explosive force at the point of controlled detonation is rendered possible in the same way as is the case with the emulsion preparation in accordance with said co-pending application.

Specifically, the water-soluble compound may be a carbon-containing compound, such as, for example, sugar, including sucrose, mannose, glucose, fructose, lactose, maltose, etc., urea, etc. Where a water-soluble oxygen-containing compound is concerned, the same may be a water-soluble metallic salt, including ammonium salts,

and in particularly nitrates, chlorates, and perchlorates.

Furthermore, the oxygen-containing compound may include, in accordance with a preferred embodiment, a water-soluble organic explosive, such as for example ethylene diamine-dinitrate, ethylene-diamine-dichlorate, ethylene diamine diperchlorate etc., such organic explosive being dissolved in water.

It will be appreciated, therefore, that the aqueous solution component of the water-in-oil emulsion preparation in accordance with the invention may be a solution of water with a member selected from the group consisting of sucrose, mannose, glucose, fructose, lactose, maltose, urea, calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate, zinc perchlorate, ethylene-diaminedinitrate, ethylene-diamine-dichlorate, ethylene-diaminediperchlorate, and mixtures thereof.

In accordance with the present invention, the water-inoil emulsion may contain up to 72% water in solution form with the foregoing water-soluble compounds, whereas the emulsifier may be present in an amount of from about 0.05 to 5% by weight based upon the total emulsion preparation, and preferably in an amount of about 1% by weight. In the same way, a stabilizer for the explosive component may be included optionally in the emulsion preparation, as for example, collodion cotton which is normally used for explosives or polyvinylacetate, e.g., with about 20 monomers in the polymer chain. The explosive component of the preparation may be in the form of a liquid or a fused compound, such as nitroglycerin or trinitrotoluene.

The emulsifier used in the preparation in accordance with the invention may be an ionic or non-ionic substance such that an aqueous solution emulsion capable of detonation is presented in which the aqueous solution phase is emulsified in the form of fine droplets in the explosive component. The water-in-oil emulsion is produced preferably with the aid of such emulsifiers, using either a liquid or fused explosive component. Regardless .of the fact that the explosive component may be liquid or solid, suitably, the explosive component must be fusible, i.e., a fusible nitrogenous explosive oil such as nitroglycerin and nitroglycol, or a fusible nitrogenous explosive solid such as trinitrotoluene. Of course, the particular emulsion prepara tion may be carried out in the conventional manner using the emulsifiers as they are added for the production of water-in-oil emulsions of the normal type.

The specific ionic emulsifier substances which may be used in accordance with the invention include the alkaline earth-, magnesium-, aluminumand zinc salts of the parafiin fatty acids, oleic acid, and the long-chain oxyacids, such as the lithium, calcium, magnesium, aluminum, and zinc salts of stearic acid, palmetic acid, oxy-stearic acid, oleic acid, and other long-chain carboxylic acids, abietic acid, etc., and mixtures thereof. On the other hand, the non-ionic emulsifier substances which may be used in accordance with the invention may include glycerine stearates, abietic acid derivatives, such as alkyl esters of abietic acid and metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, and esters of longchain fatty acids with higher alcohols, such as lanolin, etc., and mixtures thereof.

Although it is preferred that the water-in-oil emulsion contain up to 72% Water, with the emulsifier substance concentration ranging between 0.05 and 5%, preferably about 1%, based upon the emulsion, it is still possible to vary within a wide range the quantity of Water actually contained in the emulsion in solution form with the carbon-containing or oxygen-containing water soluble compound.

The following examples are set forth to establish the differences with respect to the explosive properties of the water-in-oil type emulsions of the present invention as opposed to those in which water is used alone, i.e., without the water-soluble carbon-containing compound and/or watensoluble oxygen-containing compounds of the kind noted above. It will be understood that the examples which follow are set forth for the purpose of illustrating the present invention, and the present invention is not to be limited thereby.

Example 1 A water-in-oil emulsion is produced from 50 cc. nitroglycerin (explosive oil) representing a mixture of 60 parts nitroglycerin and 40 parts nitroglycol, 50 cc. sugar-nitrate solution (containing 34.7% sugar, 27.8% Ca(NO 23.6% NH NO and 13.9% water), 0.5 gram zinc-12- oxy-stearate, and 1.0 gram collodion cotton as stabilizer. This aqueous emulsion is capable of detonation and exhibited in the lead-block according to Trauzl in a quantity of grams, a bulging of 335 cubic centimeters, the emulsion being detonated with a priming cap- #8. It is quite clear from this example that the foregoing water-inoil emulsion absolutely possesses the character of an explosive.

Example 2 Using a water-in-oil emulsion of 50 cc. nitroglycerin (explosive oil of the same type as use-d in Example 1), 50 cc. ethylene-diamine-diperchlorate solution (contain ing 56.6% ethylene-diamine-diperchlorate and 43.4% water), 0.5 gram zinc-12-oxy-stearate, and 1.0 gram collodion cotton as stabilizer, a lead block bulging of 525 cubic centimeters is obtained in accordance with the procedure of Example 1.

Example 3 Where the procedure of Example 1 is repeated using a water-in-oil emulsion produced from 50 cc. nitroglycerin (explosive oil of the same type as used in Example 1), 50 cc. water, 0.5 gram zinc-12-oxy-stearate, and 0.5 gram collodion cotton as stabilizer, but without any water-soluble carbon-containing compound or water-soluble oxygencontaining compound dissolved in the water portion, the aqueous emulsion is only capable of producing a lead block bulging of 225 cubic centimeters, as opposed to a lead block bulging of 335 cubic centimeters using a carboncontaining Water-soluble compound and an oxygen-containing water-soluble compound in accordance with Example 1 or a lead block bulging of 525 cubic centimeters uing a water-soluble organic explosive compound as the oxygen-containing compound in the Water solution in accordance with Example 2.

Therefore, it is quite clear from the foregoing examples that a Water-in-oil emulsion, capable of being detonated, may be improved considerably if the water portion of the preparation is replaced, in accordance with the invention, with an aqueous solution of a Water-soluble carbon-containing compound and/ or a water-soluble oxygen-containing compound. In accordance with a preferred embodiment of the invention, more effective results may be achieved where the water-soluble oxygen-containing compound is simultaneously a water-soluble organic explosive material.

It will be appreciated that the instant water-in-oil emulsions, i.e., wherein the water phase is represented by an aqueous solution, may be varied in the proportion of ingredients so as to vary the consistency of the preparation to be obtained, whereby pourable, creamy, foamy, syrupy, pulpy, gelatinous, pasty, fat-like or wax-like, brittle or massive solid masses may be obtained. Therefore, a versatile emulsion preparation in accordance with the invention is provided which may be safely transported, yet detonated under reasonable detonating conditions at the point of end use, using normal detonation impact values. The detonatable explosive emulsion preparation of the invention, however, represents an improved preparation over one in which the water phase consists of water along, by reason of the fact that the aqueous solution phase of the preparation in accordance with the invention leads to much higher detonation capacities than were heretofore possible.

What is claimed is:

1. Detonatable explosive emulsion preparation which comprises a water-in-oil emulsion of an aqueous solution, an emulsifier, and a nitrogenous explosive component selected from the group consisting of a fusible nitrogenous explosive oil and a fusible nitrogenous explosive solid, said aqueous solution being a solution of a water-soluble compound selected from the group consisting of calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate, zinc perchlorate, ethylenediamine-dinitrate, ethylene-diamine-dichlorate, ethylenediamine-diperchlorate, and mixtures thereof, and said emulsifier being selected from the group consisting of glycerine-stearates, alkyl esters of abietic acid, metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, esters of long chain fatty acids and higher alcohols, mixtures of the foregoing, and metal salts of long chain fatty acids.

2. Preparation according to claim 1 wherein said aqueous solution additionally includes a water-soluble compound selected from the group consisting of sucrose,

mannose, glucose, fructose, lactose, maltose, urea, and mixtures thereof.

3. Preparation according to claim 2 wherein the waterin-oil emulsion contains up to 72% water in the form of the aqueous solution, the emulsifier being present in an amount of from about 0.05 to by weight based upon the total emulsion preparation,

' 4. Preparation according to claim 3 wherein said metal salts of long chain fatty acids are selected from the group consisting of alkaline earth-, magnesium-, aluminum-, and zinc-salts of paraffin fatty acids, -oleic acid, -paraffin oxy-fatty acids, -abietic acid, and mixtures thereof.

' 5. Preparation according to claim 3 wherein a stabilizer for the explosive component selected from the group consisting of collodion cotton and polyvinyl acetate, is additionally present in the emulsion preparation.

6. Preparation according to claim 5 wherein the amount of the emulsifier is about 1% by weight and said stabilizer is collodion cotton.

7. Detonatable explosive emulsion preparation which comprises a water-in-oil emulsion of an aqueous solution, an emulsifier and nitroglycerine, said aqueous solution being a solution of a Water-soluble compound selected from the group consisting of calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, z'inc chlorate, zinc perchlorate, ethylene-diamine-dinitrate, ethylene-diamine-dichlorate, ethylene-diamine-diperchlorate, and mixtures thereof, and said emulsifier being selected from the group consisting of glycerine-stearates, alkyl esters of abietic acid, metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, esters of long chain fatty acids and higher alcohols, mixtures of the foregoing, and metal salts of long chain fatty acids.

8. Preparation according to claim 7 wherein said aqueous solution additionally includes a water-soluble compound selected from the group consisting of sucrose, mannose, glucose, fructose, lactose, maltose, urea, and mixtures thereof.

9. Detonatable explosive emulsion preparation which comprises a water-in-oil emulsion of an equeous solution, an emulsifier and trinitrotoluene, said aqueous solution being a solution of a water-soluble compound selected from the group consisting of calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate, zinc perchlorate, ethylene-diamine-dinitrate, ethylene-diamine-dichlorate, ethylene-diamine-diperchlorate, and mixtures thereof, and said emulsifier being se-.

lected from the group consisting of glycerine-stearates, alkyl esters of abietic acid, metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, esters of long chain fatty acids and higher alcohols, mixtures of the foregoing, and metal salts of long chain fatty acids.

10. Preparation according to claim 9 wherein said aqueous solution additionally includes a water-soluble compound selected from the group consisting of sucrose, mannose, glucose, fructose, lactose, maltose, urea, and mixtures thereof.

11. Detonatable explosive emulsion preparation which comprises a water-in-oil emulsion of an aqueous solution, an emulsifier and nitroglycol, said aqueous solution be-. ing a solution of a water-soluble compound selected from the group consisting of calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate, zinc.v

perchlorate, ethylene-diamine-dinitrate, ethylene-diaminedichlorate, ethylene-diamine-diperchlorate, and mixtures thereof, and said emulsifier being selected from the group consisting of glycerine-stearates, alkyl esters of abietic acid, metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, esters of long chain fatty acids and higher alcohols, mixtures of the foregoing, and metal salts of long chain fatty acids.

12. Preparation according to claim 11 wherein said aqueous solution additionally includes a water-soluble compound selected from the group consisting of sucrose, mannose, glucose, fructose, lactose, maltose, urea, and mixtures thereof.

13. Detonatable explosive emulsion preparation which comprises a water-in-oil emulsion of an aqueous solution, an emulsifier and a mixture of nitroglycerine and nitroglycol, said aqueous solution being a solution of a watersoluble compound selected from the group consisting of calcium nitrate, calcium chlorate, calcium perchlorate, sodium nitrate, sodium chlorate, sodium perchlorate, potassium nitrate, potassium chlorate, potassium perchlorate, ammonium nitrate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, magnesium perchlorate, aluminum nitrate, aluminum chlorate, barium nitrate, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate, zinc perchlorate, ethylene-diamine-dinitrate, ethylene-diaminedichlorate, ethylene-diamine-diperchlorate, and mixtures thereof, and said emulsifier being selected from the group consisting of glycerine-stearates, alkyl esters of abietic acid, metal salts of abietic acid, polyglycol ethers of ethylene oxide, adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols, esters of long chain fatty acids and higher alcohols, mixtures of the foregoing, and metal salts of long chain fatty acids.

14. Preparation according to claim 10 wherein said aqueous solution additionally includes a water-soluble compound selected from the group consisting of sucrose, mannose, glucose, fructose, lactose, maltose, urea, and mixtures thereof.

References Cited by the Examiner Young 1497 X CARL D. QUARFORTH, Primary Examiner.

LEON D- ROSDOL, xaminer.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,212,945 October 19, 1965 Adolf Berthmann et ale It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 15, for "components" read component column 2, line 3, strike out "of"; line 31, for "emulsion," rea emulsion, column 3, line 57, for "characteristic" read characteristics column 6, line 43, for "along" read alone column 7, line 49, for "equeous" read aqueous column 8, line 54, for the claim reference numeral "10" read 13 Signed and sealed this 19th day of July 1966.,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. DETONATABLE EXPLOSIVE EMULSION PREPARATION WHICH COMPRISES A WATER-IN-OIL EMULSION OF AN AQUEOUS SOLUTION, AN EMULSIFIER, AND A NITROGENOUS EXPLOSIVE COMPONENT SELECTED FROM THE GROUP CONSISTING OF A FUSIBLE NITROGENOUS EXPLOSIVE OIL AND A FUSIBLE NITROGENOUS EXPLOSIVE SOLID, SAID AQUEOUS SOLUTION BEING A SOLUTION OF A WATER-SOLUBLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CALCIUM NITRATE, CALCIUM CHLORATE, CALCIUM PERCHLORATE, SODIUM NITRATE, SODIUM CHLORATE, SODIUM PERCHLORATE, POTASSIUM NITRATE, POTASSIUM CHLORATE, POTASSIUM PERCHLORATE, AMMONIUM NITRATE, AMMONIUM CHLORATE, AMMONIUM PERCHLORATE, LITHIUM NITRATE, LITHIUM CHLORATE, LITHIUM PERCHLORATE, MAGNESIUM NITRATE, MAGNESIUM CHLORATE, MAGNESIUM PERCHLORATE, ALUMINUM NITRATE, ALUMINUM CHLORATE, BARIUM NITRATE, BARIUM CHLORATE, BARIUM PERCHLORATE, ZINC NITRATE, ZINC CHLORATE, ZINC PERCHLORATE, ETHYLENEDIAMINE-DINITRATE, ETHYLENE-DIAMINE-DICHLORATE, ETHYLENEDIAMINE-DIPERCHLORATE, AND MIXTURES THEREOF, AND SAID EMULSIFIER BEING SELECTED FROM THE GROUP CONSISTING OF GLYCERINE-STEARATES, ALKYL ESTERS OF AIETIC ACID, METAL SALTS OF ABIETIC ACID, POLYGLYCOL ETHERS OF ETHYLENE OXIDE, ADDUCTS OF HIGHER FATTY AMINES AND ETHYLENE OXIDE, POLY, VINYL ALCOHOLS, ESTERS OF LONG CHAIN FATTY ACIDS AND HIGHER ALCOHOLS, MIXTURES OF THE FOREGOING, AND METAL SALTS OF LONG CHAIN FATTY ACIDS.
 2. PREPARATION ACCORDING TO CLAIM 1 WHEREIN SAID AQUEOUS SOLUTION ADDITIONALLY INCLUDES A WATER-SOLUBLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF SUCROSE, MANNOSE, GLUCOSE, FRUTOSE, LACTOSE, MALTOSE, UREA, AND MIXTURES THEREOF. 